Method of making coated substrates
Methods' and compositions for making coated substrates using a co-solvent method are disclosed. Embodiments of the present disclosure relate in general to methods and compositions for making thin films of organometallic halides. According to one aspect, organometallic halides are deposited from solution on the surface of a substrate at temperatures between about 10 C and 50 C. According to one aspect, organometallic halides are deposited from solution on the surface of a substrate at room temperature.
1. A method of making a coated substrate comprising:
room temperature spin coating of a first solution and an organometallic halide on a surface of a substrate;
immersing the coated substrate in a room temperature bath of a second solution, the second solution causing the organometallic halide to precipitate from the first solution onto the surface, forming an organometallic halide coating;
removing the substrate from the bath; and
rapidly drying the substrate in ambient air.
2. The method of claim 1 wherein the coating of the solution is formed by applying the solution to the surface of the substrate and removing a portion of the first solvent.
3. The method of claim 1 wherein the organometallic halide is RMe n Xy wherein Me is Cu, Co, Ni, Fe, Mn, Pd, Cd, Sn, Pb, Ge, Eu or Yb; X is one or more of I, Br, Cl; y is 3 or (3n+1); n is 1, 2, 3, 4, 5; R is an organic group, CH 3 NH 3 , NH 3 CH═CH 2 , Cs, (R′—NH 3 ) 2 , (NH 3 —R′— NH 3 ) 2 or (R′— NH 3 ) 2 R (n−1) ; and R′ is alkyl, C 1 to C4 alkyl or C 6 H 5 C 2 H 4 ; with the proviso that when y is 3, n is 1, Me is Pb, Sn, Ge, Eu or Yb and R is an organic group, CH 3 NH 3 or NH 3 CH═CH 2 , or Cs, and further with the proviso that when y is (3n+1) and n is 1, Me is Cu, Co, Ni, Fe, Mn, Pd, Cd, Sn, Pb, Ge, Eu or Yb, and R is (R′— NH 3 ) 2 or (NH 3 —R′— NH 3 ) 2 and further with the proviso that when y is (3n+1) and n is 2, 3, 4, or 5, Me is Cu, Co, Ni, Fe, Mn, Pd, Cd, Sn, Pb, Ge, Eu or Yb and R is (R′— NH 3 ) 2 R (n−1) .
4. The method of claim 1 wherein the organometallic halide is RMeX 3 wherein R is an organic group or Cs, Me is Pb, Sn, Ge, Eu or Yb and X is one or more of I, Br, Cl.
5. The method of claim 1 wherein the organometallic halide is RMeX 3 wherein R is Cs or an organic group selected from the group consisting of CH 3 NH 3 or NH 2 CH═CH 2 , Me is Pb, Sn, Ge, Eu or Yb and X is one or more of Cl, Br, or I.
6. The method of claim 1 wherein the organometallic halide is CH 3 NH 3 PbI 3 .
7. The method of claim 1 wherein the organometallic halide is (R— NH 3 ) 2 MeX 4 wherein R is alkyl or C 6 H 5 C 2 H 4 , Me is a transition metal or a rare earth metal and X is one or more of Cl, Br, or I.
8. The method of claim 1 wherein the organometallic halide is (R— NH 3 ) 2 MeX 4 wherein R is C 1 to C 4 alkyl or C 6 H 5 C 2 H 4 , Me is Cu, Co, Ni, Fe, Mn, Pd, Cd, Sn, Pb Eu or Yb and X is one or more of Cl, Br, or I.
9. The method of claim 1 wherein the organometallic halide is (NH 3 —R— NH 3 ) 2 MeX 4 wherein R is alkyl or C 6 H 5 C 2 H 4 , Me is a transition metal or a rare earth metal and X is one or more of Cl, Br, or I.
10. The method of claim 1 wherein the organometallic halide is (NH 3 —R— NH 3 ) 2 MeX 4 wherein R is C 1 to C 4 alkyl or C 6 H 5 C 2 H 3 , Me is Cu, Co, Ni, Fe, Mn, Pd, Cd, Sn, Pb, Eu or Yb and X is one or more of Cl, Br, or I.
11. The method of claim 1 wherein the organometallic halide is (R′NH 3 ) 2 (R) (n−1) Me n X (3n+1) wherein R′ is C 1 to C 4 alkyl or C 6 H 5 C 2 H 4 , R is Cs, CH 3 NH 3 or NH 2 CHCH 2 , Me is Cu, Co, Ni, Fe, Mn, Pd, Cd, Sn, Pb, Eu or Yb, X is one or more of Cl, Br, or I and n is 2, 3, 4, or 5.
12. The method of claim 1 wherein the first solvent is a polar solvent having a boiling point within the range of 100° C. and 300° C.
13. The method of claim 1 wherein the first solvent is dimethylformamide, dimethylsulfoxide, γ-butyrolactone, n-methyl-2-pyrrolidone, dimethylacetamide or dimethylphosphoramide.
14. The method of claim 1 wherein the second solvent is a nonpolar solvent having a boiling point within the range of 0° C. and 100° C.
15. The method of claim 1 wherein the second solvent is diethyl ether, pentane, cyclopentane, hexane, cyclohexane, benzene, chloroform, carbon disulphide, cardon tetrachloride, dibutyl ether, diethylamine, trichloroethylene, triethylamine or dichloromethane.
16. The method of claim 1 wherein the organometallic halide precipitating onto the surface of the substrate forming a coating and the coated substrate is carried out at a temperature between 10° C. and below 70° C.
17. The method of claim 1 wherein the organometallic halide precipitating onto the surface of the substrate forming a coating and the coated substrate is carried out at a temperature between 10° C. and 50° C.
18. The method of claim 1 wherein the organometallic halide precipitating onto the surface of the substrate forming a coating and the coated substrate is carried out at a temperature of between 20° C. and 30° C.
19. The method of claim 1 wherein the organometallic halide precipitating onto the surface of the substrate forming a coating and the coated substrate is carried out at a temperature of between 18° C. and 23° C.
20. The method of claim 1 wherein the coating has a thickness of between 20 nm and 2 μm.
21. The method of claim 1 wherein the substrate surface includes one or more of a polymer, glass, ceramic, or metal.
22. The method of claim 1 wherein the second solvent extracts the first solvent forming a miscible mixture of the second solvent and the first solvent and the organometallic halide crystallizes from solution onto the surface of the substrate.
23. The method of claim 1 wherein the solution is applied to the substrate by spin coating, dip coating, spray coating, or ink jet printing.
24. The method of claim 1 wherein the first solvent and the second solvent is removed from the coated substrate.
25. The method of claim 1 wherein the coated substrate is dried at a temperature of between 18° C. and 100° C.
26. The method of claim 1 wherein the coating has an average uniform surface roughness of between about 1 nm and 20 nm (root mean square) as measured using an atomic force microscope.
27. The method of claim 1 wherein applying the second solvent to the surface of the substrate and contacting the solution is carried out by immersing the substrate in the second solvent.